JP5307320B2 - Oil-in-water sunscreen cosmetics - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-in-oil type sunscreen cosmetic which forms a cosmetic film with a high transparency, is excellent in UV-screening effect and shows an extremely improved feel at use, i.e. settles well on the skin (i.e. gets promptly fixed without running down the skin at application ) and gives a light feel without oiliness. <P>SOLUTION: The water-in-oil type sunscreen cosmetic comprises (A) a volatile organopolysiloxane, (B) a particulate metal oxide, (C) a siloxane compound essentially having an organopolysiloxane group and a long-chain alkyl group on its branch polymer in the molecule and (D) ethanol. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a water-in-oil type sunscreen formulated with a volatile organopolysiloxane, a particulate metal oxide, a specific siloxane compound essential to have an organopolysiloxane group and a long-chain alkyl group in a branched polymer, and ethanol. More particularly, the present invention relates to a water-in-oil type sunscreen cosmetic that is excellent in transparency of a cosmetic film, has a high UV-cutting effect, and has good usability.

  Conventionally, sunscreen cosmetics that protect the skin from ultraviolet rays have been blended with organic ultraviolet absorbers such as cinnamic acid compounds and benzophenone compounds, and inorganic ultraviolet shielding powders such as fine particle titanium oxide and fine particle zinc oxide. Yes.

The fine metal oxide powder can obtain a transparent and effective ultraviolet shielding effect by fine dispersion. However, since the cohesiveness between powders is strong, various powder surface treatment techniques and powder dispersants have been studied for efficient dispersion and further improvement in water resistance.
For example, a powder-in-oil dispersion using a specific nitrogen group-containing acrylic-silicone copolymer (for example, see Patent Document 1), an oil-in-water emulsion cosmetic containing a methacrylic acid-containing acrylic-silicone (for example, Patent Document) 2), a technology for imparting lubricity to cosmetics using a specific non-volatile oil agent, a silicone-based surfactant, an oil-soluble silicone resin, and a volatile solvent (for example, see Patent Document 3), a specific hydrophobizing treatment Sunscreen cosmetics using zinc powder, volatile cyclic silicone, and alkyltrimethicone (see, for example, Patent Document 4), zinc oxide containing a specific methacrylic acid-containing acrylic-silicone copolymer and a perfluoroalkyl group-containing phosphate ester A powder hydrophobization technique (see, for example, Patent Document 5) has been reported.
Japanese Patent No. 36661119 JP 2005-247722 A JP 2003-40756 A Japanese Patent Laid-Open No. 2005-232069 JP 2005-232279 A

However, when an acrylic-silicone copolymer having a specific structure is used as a dispersant, the dispersibility of the powder is very good, but stickiness peculiar to acrylic polymers may occur, and there is a problem in terms of usability. there were. In addition, a combination of a silicone-based or fluorine-based non-volatile oil agent and an oil-soluble silicone resin has considerably high water resistance, but has problems such as poor conformability to the skin and difficulty in dropping. On the other hand, the powder surface hydrophobization technology using a specific silicone treatment agent is useful for imparting a hydrophobic effect, but when it is added to the product, the surface-treated powder is redispersed again. And the selection and development of dispersants that can be easily and efficiently dispersed during the manufacturing process because the processing efficiency of the surface treatment agent has a significant impact on the stability and feel of the product. It was mandatory.
In addition, since sunscreen cosmetics are required to have a sweaty and strong finish, water-in-oil type emulsions (W / O emulsion preparations) containing volatile silicones are often used. However, when a large amount of an organic ultraviolet absorber is blended in order to enhance the ultraviolet blocking effect, the fine particle powder may aggregate due to poor compatibility with volatile silicone. Furthermore, when blending with ethanol that gives a refreshing feel, it tends to cause agglomeration of the powder, which may cause a decrease in the UV-cutting effect and whiteness of the cosmetic film. It was not yet satisfactory as a sunscreen cosmetic. Therefore, it has been desired to develop a sunscreen cosmetic that is excellent in transparency of the cosmetic film, has a high UV-cutting effect, and has good usability.

  In such a situation, the present inventors have conducted intensive research, and as a result, have found that a volatile organopolysiloxane, a particulate metal oxide, an organopolysiloxane group, and a long-chain alkyl group must be included in the branched polymer. It has been found that a water-in-oil type sunscreen cosmetic capable of solving the above-mentioned problems can be obtained by blending a siloxane compound and ethanol, and the present invention has been completed.

That is, the present invention provides the following components (A) to (D);
(A) Volatile organopolysiloxane (B) Fine particle metal oxide (C) Containing a siloxane compound (D) ethanol that must have an organopolysiloxane group and a long-chain alkyl group in the branch polymer in the molecule Is a water-in-oil type sunscreen cosmetic characterized by

The present invention also provides a water-in-oil sunscreen cosmetic, wherein the component (C) is a siloxane compound represented by the following general formula (1).
R ¹ _a R ² _b R ³ _c SiO _{(4-a-b-c) / 2} (1)
[Wherein, R ¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, an amino-substituted alkyl group, a carboxy-substituted alkyl group, or the following general formula (2)
_{-C m H 2m -O- (C 2} H 4 O) d (C 3 H 6 O) e -R 4 (2)
The same or different organic groups having at least one alkyl group having 10 or more carbon atoms as an essential component
R ² represents the following general formula (3)
_{-C m H 2m -O- (C 2} H 4 O) f (C 3 H 6 O) g -R 5 (3)
Or an organic group having a polyoxyalkylene group represented by the following general formula (4)
-QOX (4)
(In the formula, Q represents a C 3-20 divalent hydrocarbon group which may contain at least one of an ether bond and an ester bond, and X represents a polyhydric alcohol-substituted hydrocarbon group having at least two hydroxyl groups. The same or different organic groups selected from the organic groups represented by:
R ³ represents the following general formula (5)

Wherein R ⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ⁶ — (CO) —, R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Or an organic group represented by R ⁶ — (CO) —, wherein R ⁶ is a hydrocarbon group having 1 to 30 carbon atoms, d and e are integers of 0 ≦ d ≦ 50 and 0 ≦ e ≦ 50, f and g are integers of 2 ≦ f ≦ 200, 0 ≦ g ≦ 200, and f + g is 3 to 200, and h is an integer of 1 ≦ h ≦ 500, and m and n are each 0. ≦ m ≦ 15, 1 ≦ n ≦ 5, and a, b, and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5, and 0.001 ≦, respectively. c ≦ 1.5.)]

  Further, the present invention provides the water-in-oil type sunscreen makeup, wherein the component (B) is one, two or more or two or more selected from the group consisting of titanium oxide, zinc oxide and cerium oxide. It is a fee.

The water-in-oil type sunscreen cosmetics of the present invention are excellent in dispersibility of particulate metal oxides, powders do not aggregate even in a system containing an organic ultraviolet absorber, and the cosmetic film has good transparency. , Which has an excellent UV-cutting effect.
Furthermore, even if ethanol is blended, the powder remains in a good dispersion state in the cosmetic and does not aggregate over time. Therefore, when applied to the skin, the cosmetic film has excellent transparency and a good fit ( It is a water-in-oil type sunscreen cosmetic that has a significantly improved usability, such as a feeling that stops without being slicked indefinitely when applied, and a dry finish with little oiliness.

  Hereinafter, the present invention will be described in more detail.

The component (A) volatile organopolysiloxane used in the present invention includes octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane. , Methyltrimethicone, caprylyltrimethicone, and the like, and one or more can be blended depending on the purpose.
Of these, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and methyltrimethicone are preferred from the volatilization rate and powder wettability. Decamethylcyclopentasiloxane, decamethyltetrasiloxane, and methyltrimethicone are particularly preferred because of their wide spread and good makeup film size.

  Although the compounding quantity of the component (A) used for this invention is not specifically limited, It is desirable to mix | blend 5 to 35 mass% (henceforth "%" only), and 10-30% is further from a viewpoint of usability. preferable. If it is less than 5%, the proportion of the non-volatile oil in the oil system will increase, so there may be a strong feeling of oiliness after use, and if it exceeds 35%, the cosmetic film will fit too quickly. In some cases, it may be difficult to uniformly apply the sunscreen cosmetic over a large area of the body.

  The fine particle metal oxide of the component (B) used in the present invention is one having an average particle size of about 1 μm or less, preferably 0.01 to 1 μm, and further 0.01 from the ultraviolet cut effect and transparency. One type or two or more types selected from the group consisting of titanium oxide, zinc oxide, and cerium oxide of ˜0.5 μm are particularly preferable. If it exceeds 1 μm, the effect of cutting off the ultraviolet rays is reduced and the reflection of visible light is increased, so that the cosmetic film may feel white.

  The fine particle metal oxide is not particularly limited even if it is untreated or is a known surface treatment generally used in cosmetics. Examples of inorganic treatment include silica coating and alumina coating, and organic treatment includes silicone treatment, silicone resin treatment, acrylic silicone treatment, fluorine compound treatment, silane coupling agent treatment, titanium coupling agent treatment, and oil agent. Treatment, metal soap treatment and the like. Of these, silicone treatment, acrylic silicone treatment, silane coupling agent treatment, and titanium coupling agent are preferred from the viewpoint of oil absorption and ease of dispersion in the oil agent. These surface treatments may be used alone or in combination of two or more.

  Although the compounding quantity of the component (B) used for this invention is not specifically limited, It is desirable to mix | blend 0.1 to 50%, and 1 to 30% is still more preferable from usability. If it is less than 0.1%, a sufficient UV protection effect cannot be obtained, and if it exceeds 50%, the spread at the time of use may worsen, or whiteness or powderiness may appear in the cosmetic film. is there.

Although the siloxane compound which has an organopolysiloxane group and a long-chain alkyl group in the branch polymer in the molecule of the component (C) used in the present invention is not particularly limited, organic UV absorption other than organopolysiloxane From the viewpoint of good compatibility with agents and oil agents, those having a long-chain alkyl group with a carbon chain length of 10 or more are particularly preferred.
Further, the component (C) siloxane compound containing a polyoxyalkylene group or a polyglyceryl group as a hydrophilic group is particularly preferable from the viewpoint of adsorbability to the powder surface and wettability to oil.

As the siloxane compound (C), particularly preferred are those represented by the following general formula (1).
R ¹ _a R ² _b R ³ _c SiO _{(4-a-b-c) / 2} (1)
Specific examples of R ¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Hexadecyl, octadecyl, eicosyl and other alkyl groups, cyclopentyl, cyclohexyl and other cycloalkyl groups, phenyl, tolyl and other aryl groups, benzyl and phenethyl and other aralkyl groups, trifluoropropyl and hepta Fluorine-substituted alkyl groups such as decafluorodecyl group, amino-substituted alkyl groups such as 3-aminopropyl and 3-[(2-aminoethyl) amino] propyl groups, carboxy-substituted alkyl groups such as 3-carboxypropyl group, etc. is a part of R ¹ is the number 10 or more carbons of at least one or more a Kill group, specifically decyl group, consisting undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, an octadecyl group, long-chain alkyl groups such as eicosyl essential.

A part of R ¹ is represented by the following general formula (2)
_{-C m H 2m -O- (C 2} H 4 O) d (C 3 H 6 O) e -R 4 (2)
An organic group represented by Here, R ⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ⁵ — (CO) —, and R ⁵ is a hydrocarbon group having 1 to 30 carbon atoms. m is an integer of 0 ≦ m ≦ 15, and d and e are integers of 0 ≦ d ≦ 50 and 0 ≦ e ≦ 50, respectively. A part of this R ¹ is an alcohol residue or an alkenyl addition type residue.
When m = 0
_{-O- (C 2 H 4 O)} d (C 3 H 6 O) e -R 4
In this case, if d = 0 and e = 0, an alkoxy group having 4 to 30 carbon atoms, for example, a lower alkoxy group such as a butoxy group to a higher alkoxy such as an oleyloxy group such as cetyl alcohol, oleyl alcohol, and stearyl alcohol, and a stearoxy group Or fatty acid residues such as acetic acid, lactic acid, butyric acid, oleic acid, stearic acid, and behenic acid. Further, if d> 1 and e> 1, it becomes an alcohol residue of an alkylene oxide adduct of higher alcohol (terminal is a hydroxyl group).
When m ≧ 1 and d = e = 0, d is preferably 3, 5 or 11, in which case it is an allyl ether, pentenyl ether, or undecenyl ether residue, for example allyl stearyl depending on the substituent of R ⁴ Examples include ether residues, pentenyl behenyl ether residues, undecenyl oleyl ether residues, and the like. When d or e is not 0, an alkoxy group or an ester group is present via polyoxyalkylene. Whatever d and e are, when m = 0, the hydrolysis resistance may be inferior. When d is 15 or more, the oily odor is strong.

R ² represents the following general formula (3)
_{-C m H 2m -O- (C 2} H 4 O) f (C 3 H 6 O) g -R 5 (3)
Or an organic group having a polyoxyalkylene group represented by the following general formula (4)
-QOX (4)
(In the formula, Q represents a C 3-20 divalent hydrocarbon group which may contain at least one of an ether bond and an ester bond, and X represents a polyhydric alcohol-substituted hydrocarbon group having at least two hydroxyl groups. And the same or different organic groups selected from organic groups represented by
R ⁵ in the general formula (3) is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or an organic group represented by R ⁶ — (CO) —, and R ⁶ is a carbon atom having 1 to 30 carbon atoms. It is a hydrogen group. f is an integer of 2 to 200, preferably 5 to 100, g is an integer of 0 to 200, preferably 0 to 100, and f + g is 3 to 200, preferably 5 to 100. In order to impart sufficient hydrophilicity to obtain a product, it is preferable that f / g ≧ 1. In addition, when the polyoxyalkylene group shown by General formula (3) consists of both an ethylene oxide unit and a propylene oxide unit, any of the block polymer of these both units and a random polymer may be sufficient.
The Q of the general formula (4) _{in, - (CH 2) 2 -} , - (CH 2) 3 -, - CH 2 CH (CH 3) CH 2 -, - (CH 2) 4 -, - (CH 2 ) ₆ -,-(CH ₂ ) ₇ -,-(CH ₂ ) ₈ -,-(CH ₂ ) ₂ -CH (CH ₂ CH ₂ CH ₃ )-, -CH ₂ -CH (CH ₂ CH ₃ )- , — (CH ₂ ) ₃ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —O— CH ₂ CH (CH ₃ ) —, —CH ₂ —CH (CH ₃ ) —COO (CH ₂ ) ₂ — and the like can be exemplified. X is a polyhydric alcohol-substituted hydrocarbon group having at least two hydroxyl groups, and is preferably a hydrocarbon group selected from glycerin.

  Examples of glycerin include compounds represented by the following general formulas (A) to (C).

  Here, Q in the above formulas (A) to (C) is the same as Q in the general formula (3), and l and m are integers of 1 to 20. In addition, a part of the hydroxyl group in the compound may be substituted with an alkoxy group or an ester group.

R ³ represents the following general formula (5)

It is the organopolysiloxane shown by these. Here, h is 0 to 500, preferably an integer of 1 to 50. n is an integer of 1 to 5, and when synthesizing from a reaction between a vinyl group and hydrogen siloxane, n is 2. If h is greater than 500, problems such as poor reactivity with the main chain hydrogen siloxane may occur.

In the component (C) exemplified in the general formula (1) in the present invention, a is 1.0 to 2.5, preferably 1.2 to 2.3. When a is less than 1.0, the compatibility with the oil is poor, and when it is greater than 2.5, the hydrophilicity is poor. b is 0.001 to 1.5, preferably 0.05 to 1.0. If b is less than 0.001, the hydrophilicity will be poor, and if it is more than 1.5, the hydrophilicity will be too high. c is 0.001 to 1.5, preferably 0.05 to 1.0. When c is less than 0.001, the compatibility with silicone oil is poor, and when it is greater than 1.5, the hydrophilicity is poor.
Although the weight average molecular weight of the component (C) illustrated by the said General formula (1) used by this invention is not specifically limited, 500-200000 are preferable, More preferably, it is 1000-100000.

  As a commercial item of the component (C) in this invention, KF-6038 (made by Shin-Etsu Chemical Co., Ltd., display name; lauryl PEG-9 polydimethylsiloxyethyl dimethicone), KF-6105 (made by Shin-Etsu Chemical Co., Ltd., display name); Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone) and the like.

  In the present invention, the amount of the component (C) is not particularly limited, but is preferably 0.05 to 1 in terms of the mass ratio [(C) / (B)] of the component (B) to the fine particle metal oxide, 0.1 to 0.5 is particularly preferable. If the mass ratio is less than 0.05, the dispersion of the fine particle metal oxide may not be sufficiently stabilized, and as a result, the expected ultraviolet cut effect may not be obtained. Moreover, when the said mass ratio exceeds 1, a sticky feeling may be produced.

  The dispersion method of the component (B) in the present invention is not particularly limited, but the components (A) to (C), and further, if necessary, other oils and powders are mixed to perform roller treatment, ball mill, bead mill, sand mill, etc. Can be used for distributed processing. Among these, a bead mill treatment is preferable because it is excellent in finely dispersing the fine metal oxide.

The component (D) ethanol used in the present invention gives a refreshing feeling and a light feeling upon use of the sunscreen cosmetic.
The blending amount of ethanol (D) is not particularly limited, but is preferably 0.1 to 20%, and particularly preferably 1 to 10% from the feeling of use. If it is less than 0.1%, the refreshing feeling or refreshing feel of ethanol may not be sufficiently obtained, and if it exceeds 20%, the emulsion stability may be lowered.

  The cosmetics of the present invention include components used in ordinary cosmetics within a range that does not interfere with the effects of the present invention, such as oils other than component (A), surfactants, alcohols other than component (D), and moisturizing. Agents, gelling agents and thickeners, powders other than component (B), UV absorbers, antiseptics, antibacterial agents, antioxidants, skin beautifying agents (whitening agents, cell activators, anti-inflammatory agents, blood circulation promotion Agents, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, and the like.

Examples of the oil agent include natural animal and vegetable oils and semi-synthetic oils, hydrocarbon oils, ester oils, glyceride oils, silicone oils, higher alcohols, higher fatty acids and the like.
Specific examples of natural animal and vegetable oils and semi-synthetic oils include avocado oil, linseed oil, almond oil, ibtaro, eno oil, olive oil, kaya oil, carnauba wax, liver oil, kyounin oil, hydrogenated oil, wheat germ oil, sesame oil, rice germ Oil, rice bran oil, sasanqua oil, safflower oil, cinnamon oil, cinnamon oil, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, rapeseed oil, Japanese kiri oil, nuka wax, germ oil , Persic oil, palm oil, palm kernel oil, castor oil, hardened castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, jojoba oil, macadamia nut oil, cottonseed oil, coconut oil, hardened palm oil, tricoconut oil fatty acid glyceride, Peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate , Lanolin fatty acid isopropyl, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, yolk oil, and the like.
Examples of the hydrocarbon oil include squalane, squalene, ceresin, paraffin, liquid paraffin, pristane, polyisobutylene and the like.
Examples of ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, 2-ethylhexanoic acid Cetyl, ethylene glycol di-2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octoate, octyldodecyl Gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate Butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, palmitic acid 2 -Heptyl undecyl, cholesteryl 12-hydroxystearylate, dipentaerythritol fatty acid ester, isopropyl myristate, 2-octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, Examples include hexyl laurate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, and diisostearyl malate.
Examples of glyceride oil include acetoglyceride, triisooctanoic acid glyceride, triisostearic acid glyceride, triisopalmitic acid glyceride, tri-2-ethylhexanoic acid glyceride, monostearic acid glyceride, di-2-heptylundecanoic acid glyceride, and trimyristic acid. A glyceride etc. are mentioned.
Examples of the silicone oil include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, tetramethyltetrahydrogencyclotetrasiloxane, alkyl-modified silicone and the like in addition to the volatile organopolysiloxane of component (A).
Higher alcohols include cetanol, cetostearyl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, lauryl alcohol, isostearyl alcohol, 2-octyldodecanol, etc. Higher fatty acids include lauric acid, myristic acid, palmitic acid , Stearic acid, behenic acid, oleic acid, isostearic acid and the like.

The surfactant is not particularly limited as long as it is usually used in cosmetics, and any surfactant can be used. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. These may be used alone or in combination of two or more as required. They can be used in combination.
Specific examples of anionic surfactants include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and salts thereof, carboxylates such as condensation of amino acids and fatty acids, alkyl sulfonic acids, and alkene sulfones. Acid salts, sulfonates of fatty acid esters, sulfonates of fatty acid amides, sulfonates of alkyl sulfonates and their formalin condensates, alkyl sulfate esters, secondary higher alcohol sulfates, alkyl and allyl ether sulfates Ester salts, fatty acid ester sulfates, fatty acid alkylolamide sulfates, polyoxyethylene alkyl sulfates, sulfate salts such as funnel oil, alkyl phosphates, ether phosphates, alkyl allyl ether phosphates A Dorin salts, such as N- acylamino acid-based active agents.
Cationic surfactants include long chain alkyltrimethylammonium salts, dilong chain alkyldimethylammonium salts, long chain alkyldimethylbenzylammonium salts, dipolyoxyethylene alkylmethylammonium salts, dipolyoxyethylene alkyl ether dimethylammonium salts, poly Alkyl quaternary ammonium salts such as oxypropylene methyl diethyl ammonium salt and aromatic quaternary ammonium salts, pyridinium salts such as alkyl pyridinium salts, imidazoline salts such as alkyl dihydroxyethyl imidazoline salts, N-acyl basic amino acid lower alkyl esters And amine salts such as alkylamine salts, polyamines, amino alcohol fatty acid derivatives and the like.
Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxy Ethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene cured Castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene N-phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, polyoxyalkylene / alkyl co-modified organopolysiloxane, alkanolamide, sugar ether, sugar Examples include amides.
Examples of amphoteric surfactants include carbobetaine-type amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, alkyldihydroxyethylaminoacetic acid betaine, and sulfobetaine-type amphoteric surfactants such as alkylsulfobetaine, N -Amidoamine type (imidazoline type) amphoteric surfactants such as fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine salt, N-fatty acid acyl-N-carboxymethoxyethyl-N-carboxymethylethylenediamine di-salt, N- [ Amino acid type amphoteric surfactants such as 3-alkyloxy-2-hydroxypropyl] arginine salt, and alkyliminodicarboxylate type amphoteric surfactants.

  As alcohols, in addition to the component (D) ethanol, lower alcohols such as isopropanol, glycerin, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, erythritol Examples thereof include polyhydric alcohols such as saccharides, sugar alcohols such as sorbitol, maltose, xylitol and maltitol, and sterols such as cholesterol, sitosterol, phytosterol and lanosterol.

  Examples of the humectant include urea, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate and the like.

  Water-based thickeners and gelling agents include gum arabic, gum tragacanth, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), starch (rice, corn, potato, wheat), alge colloid, tolanto gum Plant polymers such as locust bean gum, microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, animal polymers such as collagen, casein, albumin, gelatin, carboxymethyl starch, methylhydroxypropyl starch, etc. Starch-based polymers, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, nito Cellulose, cellulose sulfate sodium, sodium carboxymethyl cellulose, crystalline cellulose, cellulose-based cellulose polymer, alginic acid-based polymers such as sodium alginate, propylene glycol alginate, polyvinyl methyl ether, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, etc. Vinyl polymer, polyoxyethylene polymer, polyoxyethylene polyoxypropylene copolymer polymer, acrylic polymer such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, bentonite, magnesium aluminum silicate, laponite Inorganic thickeners such as hectorite and silicic anhydride, polyethyleneimine, and cationic polymers. Also included are film forming agents such as polyvinyl alcohol and polyvinyl pyrrolidone.

  Examples of oil gelling agents include metal soaps such as aluminum stearate, magnesium stearate, zinc myristate, amino acid derivatives such as N-lauroyl-L-glutamic acid, α, γ-di-n-butylamine, dextrin palmitate, Dextrin fatty acid esters such as dextrin stearic acid ester, dextrin 2-ethylhexanoic acid palmitic acid ester, sucrose fatty acid esters such as sucrose palmitic acid ester, sucrose stearic acid ester, benzylidene of sorbitol such as monobenzylidene sorbitol, dibenzylidene sorbitol Examples thereof include organically modified clay minerals such as derivatives, dimethylbenzyl dodecyl ammonium montmorillonite clay, and dimethyl dioctadecyl ammonium montmorillonite clay.

Examples of powders include inorganic powders, organic powders, metal soap powders, colored pigments, pearl pigments, metal powders, tar dyes, natural dyes, etc., and their particle shapes (spherical, needle, plate, etc.) and particles Any one can be used regardless of the diameter (smoke, fine particles, pigment grade, etc.) and the particle structure (porous, non-porous, etc.).
As inorganic powder, in addition to the component (B) described above, zirconium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica Phlogopite, red mica, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, Examples thereof include hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, and silica.
Organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethylmethacrylate powder, cellulose powder, silk powder, nylon powder ( 12 nylon, 6 nylon), styrene / acrylic acid copolymer powder, divinylbenzene / styrene copolymer powder, vinyl resin powder, urea resin powder, phenol resin powder, fluororesin powder, silicon resin powder, acrylic resin powder, melamine Resin powder, epoxy resin powder, polycarbonate resin powder, microcrystalline fiber powder powder, comedemp And lauroyl lysine.
Examples of metal soap powder (surfactant metal salt powder) include zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, and sodium zinc cetyl phosphate. Each powder is mentioned.
Examples of colored pigments include inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and loess, black iron oxide, carbon black, etc. Lake inorganic black pigments, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as bitumen and ultramarine blue, and tar dyes And those obtained by lacquering natural pigments and composite powders obtained by combining these powders.
Examples of the pearl pigment include titanium oxide coated mica, titanium oxide coated mica, bismuth oxychloride, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, fish scale foil, titanium oxide coated colored mica, and the metal powder. Examples thereof include aluminum powder, copper powder, and stainless steel powder.
As tar pigments, Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 204, Yellow 401, Blue 1, Blue 2, Blue 201, Blue 404 , Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207 and the like. , Calsamine, bradylin, crocin and the like.
These powders may be used as they are, but they may be used by combining the powders or performing surface treatment with an oil agent, silicone, fluorine compound or the like.
The powders can be used alone or in combination of two or more as required.

  Examples of UV absorbers include benzoic acid UV absorbers such as paraaminobenzoic acid, anthranilic UV absorbers such as methyl anthranilate, salicylic acid UV absorbers such as methyl salicylate, and cinnamon such as octyl paramethoxycinnamate. Examples thereof include acid ultraviolet absorbers, benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone, urocanic acid ultraviolet absorbers such as ethyl urocanate, and the like.

  Preservatives and antibacterials include paraoxybenzoic acid esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, salicylic acid, coalic acid, sorbic acid, parachlormetacresol, hexachlorophene, benzalkonium chloride, chloride Examples include chlorhexidine, trichlorocarbanilide, photosensitizer, and isopropylmethylphenol.

  Antioxidants include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, and pH adjusters include lactic acid, lactate, citric acid, citrate, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, hydrogen carbonate Sodium, ammonium bicarbonate, etc., chelating agents such as alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphate, hydroxyethane diphosphone, etc., and refreshing agents such as L-menthol, camphor, light cargo oil, peppermint Examples of anti-inflammatory agents such as oil and eucalyptus oil include allantoin, glycyrrhetinate, glycyrrhetin derivatives, tranexamic acid, and azulene.

  As skin beautifying ingredients, whitening agents such as arbutin, glutathione, and yukinoshita extract, royal jelly, photosensitizer, cholesterol derivatives, cell activators such as calf blood extract, rough skin improving agent, nonyl acid wallenyl amide, nicotinic acid benzyl ester, Nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin , Blood circulation promoters such as γ-oryzanol, skin astringents such as zinc oxide and tannic acid, and antiseborrheic agents such as sulfur and thianthol.

  Vitamins such as vitamin A oil, retinol, retinol acetate, retinol palmitate, etc., vitamin B2 such as riboflavin, riboflavin butyrate, flavin adenine nucleotide, vitamin B6 such as pyridoxine hydrochloride, pyridoxine dioctanoate Vitamins such as L-ascorbic acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sodium sulfate, dl-α-tocopherol-L-ascorbic acid diester dipotassium, calcium pantothenate, Pantothenic acids such as D-pantothenyl alcohol, pantothenyl ethyl ether, acetyl pantothenyl ethyl ether, vitamin Ds such as ergocalciferol and cholecalciferol, nicotinic acid, benzyl nicotinate Nicotinic acids such as nicotinic acid amide, dl-α-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol nicotinate, vitamin E such as dl-α-tocopherol succinate, vitamin P, biotin, etc. .

  Examples of amino acids include arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine, isoleucine, tryptophan, alanine, glycine, proline and the like, nucleic acids such as deoxyribonucleic acid, and hormones such as estradiol and ethinylestradiol.

  The water-in-oil type sunscreen cosmetic of the present invention can be prepared by a conventional method using other components in combination as necessary, for example, liquid, emulsion, cream, solid, gel, paste Etc., and can be implemented in various forms. Moreover, the water-in-oil type sunscreen cosmetics of the present invention can be implemented in products such as sunscreen emulsions and creams, makeup bases and foundations.

  The following examples further illustrate the present invention. In addition, these do not limit this invention at all.

Examples 1-4 and Comparative Examples 1-6
With the composition shown in Table 1, a bead-milled fine particle zinc oxide dispersion-treated product was prepared. Furthermore, a water-in-oil type sunscreen emulsion having the composition shown in Table 2 was prepared using this dispersion. Transparency of each water-in-oil type sunscreen emulsion, UV-blocking effect, stability, sensory evaluation, good comfort when applied to the skin (propensity to stay without slicking at the time of application), lack of oiliness, The finish and the transparency of the decorative film were evaluated and evaluated by the following evaluation method. The results are also shown in Table 2.

Note 1: KF-6038 (Shin-Etsu Chemical Co., Ltd.)
Note 2: KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 3: KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 4: KF-6104 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 5: KF-6019 (manufactured by Shin-Etsu Chemical Co., Ltd.)

Note 6: KF-96A-10cs (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Evaluation of transparency)
A thin film of a water-in-oil type sunscreen emulsion having a thickness of 6 μm was formed on a quartz plate, the transmission spectrum was measured, and the transmittance at 400 nm was used as an index of transparency. Here, the higher the transmittance of visible light 400 nm, the higher the transparency.
(Evaluation of UV protection effect)
In the transmission spectrum of each of the above water-in-oil sunscreen emulsions, the transmittance of 360 nm was used as an index of the ultraviolet cut effect. Here, the lower the transmittance at 360 nm in the UVA region, the higher the ultraviolet cut effect.
(Evaluation of stability)
The water-in-oil type sunscreen cosmetics were allowed to stand at 40 ° C. for 2 weeks and then shaken 20 times, and changes in appearance (texture, viscosity changes) were determined according to the following criteria.

(Transparency judgment)
◎: 400 nm transmittance 95% or more ○: 400 nm transmittance 90% or more but less than 95% Δ: 400 nm transmittance 85% or more but less than 90% ×: 400 nm transmittance less than 85%

(UV cut effect judgment)
◎: 360 nm transmittance 5% or less ○: 360 nm transmittance 5% or more and less than 10% Δ: 360 nm transmittance 10% or more but less than 15% ×: 360 nm transmittance 15% or more

(Stability judgment)
○: No change in appearance △: Slight change in appearance (slightly poor texture, slightly increased viscosity)
×: Change in appearance (bad texture, thickened gel)

<Sensory test>
About 10 samples of the professional panel, each sample of Examples 1 to 4 and Comparative Examples 1 to 6 has good comfort when applied to the skin (feels that it does not slick without lingering when applied), lack of oiliness, The test was performed for each evaluation item of the finished finish and transparency of the decorative film, each panel gave a score using the following evaluation criteria a, and the average value was calculated from the total score of all panel members for each sample Was determined using the following criteria b.

(Evaluation criteria a)
(Score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad

(Criteria b)
(Judgment): (Average score)
◎: Over 5 points ○: Over 4.5 points and 5 points or less △: Over 2.5 points and 4.5 points or less ×: 2.5 points or less

(Production method)
A: After components 10-14 are mixed uniformly, components 1-9 are added and sufficiently dispersed.
B: Components 15 to 19 are mixed uniformly.
C: Emulsified while adding B to A to obtain a water-in-oil sunscreen emulsion.

As is clear from the results in Table 2, the water-in-oil type sunscreen emulsions of Examples 1 to 4 were transparent and excellent in ultraviolet ray blocking effect and emulsion stability. Also, when applied to the skin, it shows good results in all items, such as a smoothness that does not slick when applied to the skin, lack of oiliness, a smooth finish, and transparency when actually applied to the skin And proved to be an excellent water-in-oil sunscreen emulsion.
On the other hand, Comparative Examples 1 to 6 were not satisfactory in all items, and Comparative Examples 1 to 4 using a silicone surfactant containing an organopolysiloxane group not containing a long-chain alkyl group in a branched polymer. It was inferior in the ultraviolet ray cut effect and transparency. In addition, Comparative Examples 1 and 2 using fine zinc oxide are more UV-blocking effect and transparency than those of Comparative Examples 3 and 4 using silicone surface-treated fine zinc oxide, and the feeling of use by sensory evaluation when applied to the skin. It was inferior. In Comparative Example 5 using a silicone-based surfactant having no long-chain alkyl group and organopolysiloxane group in the branched polymer, satisfactory results were not obtained in all items. Moreover, the comparative example 6 which does not contain ethanol was especially inferior to the goodness of use at the time of use, and the smooth finish.

Example 5: Water-in-oil sunscreen cream A water-in-oil sunscreen cream was prepared by the following composition and production method.
(composition)
(Ingredient) (%)
1. Methyl trimethicone 5
2. Acrylic-silicone-treated fine particle titanium oxide (Note 7) 5
3. Lauryl PEG-9 polydimethylsiloxyethyl dimethicone (Note 1) 0.5
4). Dimethylpolysiloxane (Note 8) 2
5. Trimethylsiloxysilicic acid /
Decamethylcyclopentasiloxane solution (Note 9) 5
6). Inulin stearate (Note 10) 2
7). Octyl paramethoxycinnamate 3
8). Diethylaminohydroxybenzoyl hexyl benzoate 0.5
9. Cetyl 2-ethylhexanoate 5
10. PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) 2
11. Ethanol 10
12 Glycerin 2
13. Sodium chloride 1
14 Preservative appropriate amount15. Silicone composite spherical powder (Note 11) 2
16. Perfume appropriate amount 17. Purified water remaining

Note 7: KF-549 (manufactured by Shin-Etsu Chemical Co., Ltd.) treated fine particle titanium oxide (average particle size 0.02 μm)
Note 8: KF96A-2cs (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 9: KF-7712J (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 10: Leopard ISK (Chiba Flour Mills)
Note 11: KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Manufacturing method)
A: Components 1 to 3 are subjected to bead mill treatment and uniformly dispersed.
B: Ingredients 4 to 10 are heated and dissolved, A is added and mixed uniformly, and 15 is mixed and dissolved uniformly.
C: Components 11 to 14 and component 17 are mixed and dissolved.
D: Cooling after emulsification while adding C to B.
E: Components 15 and 16 were added to D and mixed uniformly to obtain a water-in-oil sunscreen cream.

  The water-in-oil type sunscreen cream of Example 5 obtained as described above has a good fit when applied to the skin, a refreshing finish without oiliness, and excellent transparency and UV-blocking effect. Also, the excellent stability was exhibited.

Example 6: Sunscreen makeup base A sunscreen makeup base was prepared by the following composition and production method.
(composition)
(Ingredient) (%)
1. Cross-linked methylpolysiloxane /
Decamethylcyclopentasiloxane compound (Note 12) 15
2. Acrylic-silicone graft copolymer /
Decamethylcyclopentasiloxane solution (Note 13) 1
3. Decamethylcyclopentasiloxane 7
4). Organopolysiloxane-treated fine zinc oxide (Note 14) 3
5. Organopolysiloxane-treated fine particle titanium oxide (Note 15) 1
6). Lauryl polyglyceryl-3
Polydimethylsiloxyethyl dimethicone (Note 3) 1
7). Octyl paramethoxycinnamate 5
8). Liquid paraffin 3
9. Cetyl polyether-modified silicone (Note 16) 2
10. Ethanol 2
11.1,3-butylene glycol 7
12 Spherical silica powder 1
13. Cross-linked acrylamide copolymer dispersion (Note 17) 0.3
14 Preservative appropriate amount15. Perfume appropriate amount 16. Purified water remaining

Note 12: KSG-15 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 13: KP-545 (Shin-Etsu Chemical Co., Ltd.)
Note 14: Methyl hydrogen polysiloxane-treated fine particle zinc oxide (average particle size 0.02 μm)
Note 15: Methyl hydrogen polysiloxane-treated fine particle titanium oxide (average particle size 0.02 μm)
Note 16: Avil EM-90 (Gold Schmidt)
Note 17: Sepigel 305 (manufactured by Sepic)

(Manufacturing method)
A: Components 1 to 6 are roller-processed and mixed uniformly.
B: A is added to components 7 to 9 and mixed.
C: Components 10 to 14 and 16 are mixed uniformly.
D: After emulsification while adding C to B, component 15 was added and mixed uniformly to obtain a sunscreen makeup base.

  The sunscreen makeup base of the product 6 of the present invention obtained as described above has a good finish when applied to the skin, a refreshing finish without oiliness, excellent transparency and UV blocking effect, stable In addition, the effect was extremely excellent.

Example 7: Water-in-oil liquid foundation A water-in-oil liquid foundation was prepared by the following composition and production method.
(composition)
(Ingredient) (%)
1. Dodecamethylcyclohexasiloxane 10
2. Methyl trimethicone 5
3. Dimethylpolysiloxane (Note 18) 5
4). Organopolysiloxane-treated fine particle titanium oxide (Note 14) 5
5. Organopolysiloxane-treated titanium oxide (Note 19) 7
6). Bengala treated with organopolysiloxane (Note 20) 0.5
7). Organopolysiloxane-treated yellow iron oxide (Note 21) 1.4
8). Black iron oxide treated with organopolysiloxane (Note 22) 0.1
9. Mica treated with organopolysiloxane (Note 23) 3
10. Lauryl PEG-9 polydimethylsiloxyethyl dimethicone (Note 1) 2.5
11. Rosin acid pentaerythritol 3
12 Diisostearyl malate 3
13. Octyl paramethoxycinnamate 2
14 Polyglyceryl-3 polydimethylsiloxyethyl dimethicone (Note 4) 1
15.1,3-Butylene glycol 3
16. Ethanol 7
17. Hydromethoxybenzophenonesulfonic acid 0.2
18. Antiseptic suitable amount 19. Purified water remaining amount 20. Perfume

Note 18: KF-96A-6cs (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 19: SA-titanium CR-50 (manufactured by Miyoshi Kasei Co., Ltd.)
Note 20: SA-Bengara Cloisonne (manufactured by Miyoshi Kasei Co., Ltd.)
Note 21: SA-yellow lemon (manufactured by Miyoshi Kasei Co., Ltd.)
Note 22: SA-Black BL-100 (manufactured by Miyoshi Kasei Co., Ltd.)
Note 22: SA-Sericite FSE (manufactured by Miyoshi Kasei)

(Manufacturing method)
A: Roll components 1 to 10 and mix uniformly.
B: Components 11 to 14 are mixed and dissolved uniformly, and A is added and mixed.
C: Components 15 to 19 are mixed and dissolved uniformly.
D: After emulsification while adding C to B, component 20 was added and mixed uniformly to obtain a water-in-oil liquid foundation.

  The water-in-oil liquid foundation of Example 7 obtained as described above has a good fit when applied to the skin, a refreshing finish with no oiliness, and a natural cosmetic film and UV-blocking effect. It was excellent and showed an extremely excellent effect in stability.

Claims (7)

The following components (A) to (D);
(A) Volatile organopolysiloxane (B) Fine particle metal oxide (C) Oil blended with a siloxane compound (D) ethanol, which essentially has an organopolysiloxane group and a long-chain alkyl group in the branch polymer in the molecule Medium water type sunscreen cosmetics,
The compounding amount of the component (B) is 1 to 30% by mass,
The mass ratio [(C) / (B)] of component (C) to component (B) is 0.1 to 0.5,
A water-in-oil type sunscreen cosmetic, wherein the component (C) is a siloxane compound represented by the following general formula (1 ') and further contains an oil selected from glyceride oils.
^{_{R 1 a R 2 'b R}} 3 c SiO (4-abc) / 2 (1')
[Wherein R ¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, an amino-substituted alkyl group, a carboxy-substituted alkyl group, or the following general formula (2)
_{-C m H 2m -O- (C 2} H 4 O) d (C 3 H 6 O) e -R 4 (2)
The same or different organic groups having at least one alkyl group having 10 or more carbon atoms as an essential component
R ² 'is the following general formula (4)
-QOX (4)
(In the formula, Q represents a C 3-20 divalent hydrocarbon group which may contain at least one of an ether bond and an ester bond, and X represents a polyhydric alcohol-substituted hydrocarbon group having at least two hydroxyl groups. The same or different organic groups selected from the organic groups represented by:
R ³ represents the following general formula (5)
Wherein R ⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ⁵ — (CO) —, and R ⁵ is a hydrocarbon having 1 to 30 carbon atoms. D and e are integers of 0 ≦ d ≦ 50 and 0 ≦ e ≦ 50, h is an integer of 1 ≦ h ≦ 500, and m and n are 0 ≦ m ≦, respectively. An integer of 15 and an integer of 1 ≦ n ≦ 5, and a, b, and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5, and 0.001 ≦ c ≦ 1, respectively. .5))] The water-in-oil type sunscreen makeup according to claim 1, wherein the particulate metal oxide of component (B) is one or more selected from the group consisting of titanium oxide, zinc oxide and cerium oxide. Fee. The water-in-oil type sunscreen cosmetic according to any one of claims 1 and 2, wherein the component (B) is a fine particle metal oxide having an average particle size of 0.01 to 1 µm. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 3, wherein the amount of the component (A) is 5 to 35% by mass. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 4, wherein the amount of the component (D) is 0.1 to 20% by mass. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 5, wherein the blending amount of the component (B) is 20% by mass or more. It is a manufacturing method of the water-in-oil type sunscreen cosmetics of any one of Claims 1-6,
The manufacturing method characterized by including the process of dispersing a component (B) in a component (A) by using a component (C) as a dispersing agent.